Synthesis of Zeolite with the CHA Crystal Structure, Synthesis Process and Use Thereof for Catalytic Applications

ABSTRACT

Disclosed is a synthesis process of a crystalline material with the CHA structure, which comprises the following steps: i) Preparation of a mixture that comprises one source of water, one source of a tetravalent element Y, one source of an alkaline or alkaline earth cation (A), one source of a trivalent element X, and one organic molecule (OSDA1) with the structure [R1R2R3R4N+]Q−, being the molar composition: n X2O3:YO2:a A:m OSDA1:z H2O, ii) crystallisation of the mixture obtained in i) in a reactor, iii) recovery of the crystalline material obtained in ii).

DESCRIPTION Field of the Invention

The present invention relates to a new synthesis process of zeolite withthe chabazite crystal structure, as well as to the use of the zeolitematerial synthesised according to the present synthesis process as acatalyst.

Background

Zeolites, or molecular sieves, are described as materials formed by TO₄tetrahedra (T=Si, Al, P, Ge, B, Ti, Sn, etc.), interconnected by oxygenatoms, to create pores and cavities of uniform size and shape over themolecular range. These zeolite materials have important applications ascatalysts, adsorbents or ion exchangers, amongst others.

Zeolites may be classified on the basis of the size of their channelsand pores. In this regard, zeolites with channels limited by 8-T atomsare called “small-pore zeolites” (openings of about 4 Å), zeolites withchannels limited by 10-T atoms are “medium-pore zeolites” (openings ofabout 5.5 Å), those with channels limited by 12-T atoms are “large-porezeolites” (openings of about 7 Å), and, finally, zeolites with channelslimited by more than 12-T atoms are called “extra-large-pore zeolites”(openings greater than 7 Å).

Amongst the more than 200 zeolite structures accepted by theInternational Zeolite Association (IZA), the chabazite crystal structureis one of the most interesting, due to its use in many diverseapplications, most noteworthy as a heterogeneous catalyst inmethanol-to-olefins processes (MTO) and in the selective catalyticreduction (SCR) of NOx.

The IZA has assigned the code CHA to the molecular sieve chabazite,which has a crystal structure formed by a tri-directional system ofsmall pores interconnected by large cavities. The CHA structure has beensynthesised with various chemical compositions, most noteworthy as analuminosilicate (“SSZ-13”; Zones, U.S. Pat. No. 4,544,538, 1985,assigned to Chevron) or silicoaluminophosphate (“SAPO-34”; Lok et al.,U.S. Pat. No. 4,440,871, 1984, assigned to UOP).

In general, it may be said that aluminosilicates show higherhydrothermal stability and better acidic properties than homologoussilicoaluminophosphates (Katada et al., J. Phys. Chem. C., 2011, 115,22505). Consequently, the synthesis of the CHA structure inaluminosilicate form, in an economical manner and with goodphysical-chemical properties, would be of great interest for applicationin industrial processes.

Chabazite is a natural zeolite that has the following chemicalcomposition: Ca₆Al₁₂Si₂₄O₇₂. In addition to the natural form ofchabazite, this zeolite structure has been synthesised in the laboratoryusing different inorganic alkaline cations as inorganicstructure-directing agents (SDAs). Thus, the following syntheses havebeen disclosed: zeolite K-G (J. Chem. Soc., 1956, 2822), which is achabazite synthesised in the presence of potassium cations and has anSi/Al ratio of 1.1-2.1; zeolite D (British Patent 868846, 1961), whichis a chabazite synthesised in the presence of sodium-potassium cationsand has an Si/Al ratio of 2.2-2.5; and zeolite R (U.S. Pat. No.3,030,181, 1962, assigned to Union Carbide), which has an Si/Al ratio of1.7-1.8.

Most likely, the first use of organic structure-directing agents (OSDAs)in the synthesis of the zeolite chabazite was disclosed by Tsitsishriliet al. (Soobsch. Akad. Nauk. Cruz, SSR, 1980, 97, 621), who show thepresence of tetramethylammonium (TMA) cations in the reaction mixtureK₂O—Na₂O—SiO₂—Al₂O₃—H₂O. However, the Si/Al ratio obtained in the finalsolid is very low (Si/Al˜2.1). The article discloses that the presenceof TMA in the synthesis medium seems to affect the crystallisation ofCHA, but said organic molecule is not incorporated into the synthesisedmaterial.

In general, aluminosilicates with a low Si/Al ratio (lower than 5)exhibit low hydrothermal stability. Consequently, in order to increasesaid Si/Al ratio in the synthesis of CHA, larger OSDAs, such asN,N,N-tri-alkyl-1-adamantylammonium, N-alkyl-3-quinuclidinol and/orN,N,-tri-alkyl-exoaminonorbornane (Zones, U.S. Pat. No. 4,544,538, 1985,assigned to Chevron), were introduced into the synthesis medium. Usingthese OSDAs, the zeolite CHA is obtained with Si/Al ratios rangingbetween 4-25, which is called SSZ-13.

The preferred OSDA for the synthesis of the zeolite SSZ-13 is theN,N,N-tri-methyl-1-adamantammonium (TMAdA) cation. However, said OSDAhas a high cost. This high cost may limit the commercial use of thezeolite SSZ-13 in industrial processes. Therefore, the synthesis of thezeolite SSZ-13 using more economical OSDAs would be of great interestfor potential commercial applications of said zeolite.

An alternative for reducing the content of the TMAdA cation in thepreparation of the zeolite SSZ-13 involves introducing mixtures of TMAdAwith another, more economical OSDA, such as benzyltrimethylammonium(Zones, U.S. Patent 2008/0075656, 2008, assigned to Chevron). In thisinvention, the TMAdA content is significantly reduced by introducing thebenzyltrimethylammonium cation into the synthesis medium. Despite thecost reduction when preparing the zeolite SSZ-13 using these mixtures ofOSDAs, the presence of the TMAdA cation, which has a high cost, is stillnecessary.

Similarly, the use of mixtures of the OSDAs TMAdA andtetramethylammonium (TMA) in the synthesis medium has been proposed tosynthesise the aluminosilicate form of CHA (Bull et al., WO2011/064186,2011, assigned to BASF). Despite the cost reduction when preparing thezeolite SSZ-13 using these mixtures of OSDAs, the presence of the TMAdAcation, which has a high cost, is still necessary.

Recently, the synthesis of the aluminosilicate form of CHA using new,more economical organic molecules than the original OSDA TMAdA as theonly OSDAs in the synthesis medium has been disclosed. Said organicmolecules are benzyltrimethylammonium (Miller et al., U.S. Pat. No.8,007,764, 2011, assigned to Chevron), cycloalkyl ammoniums (Cao et al.,U.S. Patent 2008/0045767, 2008, assigned to ExxonMobil; Feyen et al.,WO2013/182974, 2013, assigned to BASF), N,N-dimethylpiperidinium (Yilmazet al., WO2013/035054, 2013, assigned to BASF), andN-alkyl-1,4-diazabicyclo[2.2.2]octane cations and derivatives thereof(Zones, WO2010/114996, 2010, assigned to Chevron).

In addition to the OSDAs described above, recently the synthesis of thealuminosilicate form of CHA using choline has also been disclosed (Chenet al., Environ. Sci. Technol., 2014, 48, 13909). In said publication,the authors claim that the use of choline allows for an economicalpathway to synthesise CHA. However, for the efficient synthesis of amaterial, and its subsequent commercial application in industry, notonly the sources used in the preparation thereof must be economicallyappealing, but the material preparation process must also exhibit goodyields. In this case, the starting Si/Al ratio of the material is 20 (asmay be calculated from the experimental synthesis process of SSZ-13described in the publication); however, the final Si/Al ratio of thecrystalline solid obtained is 6.5. Said difference suggests that thesynthesis yield is less than 30% (crystalline solid obtained as afunction of the inorganic oxides introduced during preparation of thegel). This low yield would prevent the use of said synthesis process inpotential industrial applications.

In recent years, it has been disclosed that zeolite materials with theCHA crystal structure wherein Cu cations have been incorporated (Cu-CHA)are efficient heterogeneous catalysts for the selective reduction of NOxin transport-related emissions. These catalysts show high hydrothermalstability thanks to the presence of the small pores of the CHAstructure, and the stabilisation of the Cu cations in the CHA cavities.These catalysts are capable of tolerating temperatures greater than 700°C. in the presence of water.

Despite the progress observed in recent years in the synthesis of thezeolite SSZ-13 using more economical OSDAs, there is clearly still aneed for the chemical industry to improve the synthesis of said crystalstructure, with a view to its application in various catalyticapplications, and, more particularly, its use as a catalyst and/orsupport in the treatment of NOx in gas emissions from automobiles.

DESCRIPTION OF THE INVENTION

The present invention relates to a new synthesis process of a zeolitewith the chabazite structure (CHA), which uses a commercial andeconomical OSDA, as well as the subsequent use of the zeolitesynthesised as a catalyst in various catalytic processes, such asmethanol to olefins and the selective catalytic reduction (SCR) of NOxin gas emissions.

The present invention relates to a new synthesis process of acrystalline material with the CHA zeolite structure, which may comprise,at least, the following steps:

-   -   i) Preparation of a mixture that comprises at least one source        of water, at least one source of a tetravalent element Y, at        least one source of an alkaline or alkaline earth cation A, at        least one source of a trivalent element X, and at least one        organic molecule (OSDA1) with the structure [R¹R²R³R⁴N⁺]Q⁻,    -   wherein R¹, R², R³ and R⁴ are selected from linear alkyl groups,        and    -   wherein R¹, R², R³ and R⁴ each have between 1 and 4 carbon        atoms, but at least two of them must have at least two carbon        atoms, and wherein Q⁻ is an anion, being the molar composition:

n X₂O₃:YO₂:a A:m OSDA1:z H₂O

wherein

-   -   n ranges between 0 and 0.1; preferably between 0.005 and 0.1;        and, more preferably, between 0.01 and 0.1.    -   a ranges between 0 and 2; preferably between 0 and 1; and, more        preferably, between 0 and 0.8.    -   m ranges between 0.01 and 2; preferably between 0.1 and 1; and,        more preferably, between 0.1 and 0.6.    -   z ranges between 1 and 200; preferably between 1 and 50; and,        more preferably, between 2 and 20.    -   ii) Crystallisation of the mixture obtained in i) in a reactor    -   iii) Recovery of the crystalline material obtained in ii)

According to a particular embodiment, the source of the tetravalentelement Y may be selected from silicon, tin, titanium, germanium, andcombinations thereof. Preferably, the source of the element Y is asource of silicon that may be selected from silicon oxide, siliconhalide, colloidal silica, fumed silica, tetraalkyl orthosilicate,silicate, silicic acid, a previously synthesised crystalline material, apreviously synthesised amorphous material, and combinations thereof;and, more preferably, it is a material selected from a previouslysynthesised crystalline material, a previously synthesised amorphousmaterial and combinations thereof; and, more preferably, a previouslysynthesised crystalline material.

Some examples of previously synthesised materials may be faujasite-type(FAU) and L-type (LTL) zeolites, and amorphous ordered mesoporousmaterials, such as MCM-41. These previously synthesised materials mayfurther contain other heteroatoms in their structure, such as, forexample, aluminium.

According to a particular embodiment, the source of the element Y may bea previously synthesized material, faujasite, and may containheteroatoms in its structure, such as, for example, aluminium.

According to a preferred embodiment, the source of the trivalent elementX may be selected from aluminium, boron, iron, indium, gallium andcombinations thereof.

According to a particular embodiment, the trivalent element X isaluminium. Said source of aluminium may be selected from, at least, anyaluminium salt (for example, aluminium nitrate) or any hydrated aluminumoxide.

According to a particular embodiment of the present invention, OSDA1 maybe selected from tetraethylammonium, methyl triethylammonium, propyltriethylammonium, diethyl dipropylammonium, diethyl dimethylammonium,and combinations thereof. Preferably, said OSDA1 is tetraethylammonium.

The present invention shows the use of simple organic molecules such asOSDAs in the synthesis of zeolite with the chabazite structure, based ontetraalkylammonium cations, wherein the alkyl groups are linear chainsranging between C1 and C4, and where, at least, two of said alkyl groupsare a C2 or longer linear chain.

Particularly, it is shown that the tetraethylammonium (TEA) cationallows for the synthesis of zeolite with the chabazite structure with alow economic cost, since said organic molecule is commercial and,furthermore, requires precursors that are much more economical thanthose required for the preparation of many of the more complex organicmolecules described above for the synthesis of a zeolite with thechabazite structure. Moreover, the present process allows obtaining thedesired crystalline material with high yields (greater than 80%).

According to the present invention, the crystallisation processdescribed in ii) is preferably performed in autoclaves, under conditionsthat may be static or dynamic, at a temperature ranging between 100° C.and 200° C., preferably between 130° C. and 175° C., and, morepreferably, between 150° C. and 175° C., and with a crystallisation timeranging between 6 hours and 50 days, preferably between 1 and 14 days,and, more preferably, between 2 and 10 days. It must be borne in mindthat the components of the synthesis mixture may come from differentsources, which may modify the crystallisation conditions described.

According to a particular embodiment of the process of the presentinvention, CHA crystals may be added to the synthesis mixture to act asseeds, thus favouring the synthesis described, in a quantity of up to25% by weight with respect to the total quantity of oxides. Thesecrystals may be added before or during the crystallisation process.

According to the process described, following the crystallisationdescribed in ii), the resulting solid is separated from the motherliquour and recovered. Recovery step iii) may be performed by means ofdifferent known separation techniques, such as, for example,decantation, filtration, ultrafiltration, centrifugation or any othersolid-liquid separation technique, and combinations thereof.

The process of the present invention may further comprise theelimination of the organic content retained inside the material by meansof an extraction process.

According to a particular embodiment, the elimination of the organiccompound retained inside the material may be performed by means of aheat treatment at temperatures greater than 25° C., preferably rangingbetween 100° C. and 1000° C., for a period of time preferably rangingbetween 2 minutes and 25 hours.

According to another particular embodiment, the material produced inaccordance with the present invention may be pelletized using any knowntechnique.

In the process described above, any cation present in the material maybe exchanged with other cations by means of ion exchange usingconventional techniques. Thus, depending on the X₂O₃/YO₂ molar ratio ofthe synthesised material, any cation present in the material may beexchanged, at least partially, by means of ion exchange. These exchangedcations are preferably selected from metals, protons, proton precursors(such as, for example, ammonium ions) and mixtures thereof; morepreferably, said cation is a metal selected from rare earths, metals ofgroups IIA, IIIA, IVA, VA, IB, IIB, IIIB, IVB, VB, VIB, VIIB, and VIII,and combinations thereof.

According to a preferred embodiment, the ion exchange cation is copper.

The present invention also relates to a zeolite material with the CHAstructure obtained according to the process described above, which mayhave the following molar composition:

o X₂O₃:YO₂:p A:q OSDA1:r H₂O

wherein

-   -   X is a trivalent element;    -   Y is a tetravalent element;    -   A is an alkaline or alkaline earth cation;    -   o ranges between 0 and 0.1; preferably between 0.005 and 0.1;        and, more preferably, between 0.01 and 0.1.    -   p ranges between 0 and 1, preferably between 0 and 0.8; and more        preferably between 0 and 0.5.    -   q ranges between 0.01 and 1; preferably between 0.01 and 0.5;        and, more preferably, between 0.01 and 0.3.    -   r ranges between 0 and 2; preferably between 0 and 1.5; and,        more preferably, between 0 and 1.

According to a preferred embodiment, the material obtained according tothe present invention may be calcined. Thus, the zeolite material withthe CHA structure may have the following molar composition after beingcalcined:

o X₂O₃:YO₂

wherein

-   -   X is a trivalent element;    -   Y is a tetravalent element; and    -   o ranges between 0 and 0.1; preferably between 0.005 and 0.1;        and, more preferably, between 0.01 and 0.1.

According to a particular embodiment, the tetravalent element Y of thezeolite material with the CHA structure may be preferably selected fromsilicon, tin, titanium, germanium, and combinations thereof; morepreferably, it is silicon.

On the other hand, the trivalent element X of the zeolite material withthe CHA structure according to the present invention may be preferablyselected from aluminium, boron, iron, indium, gallium and combinationsthereof; more preferably, it is Al.

The material of the present invention obtained according to the processdescribed above has the lattice structure of the zeolite CHA.

According to a particular embodiment, the crystalline material obtainedis substantially free from the presence of phosphorus in the crystallattice.

The present invention also relates to the use of the materials describedabove, obtained according to the process of the present invention, ascatalysts for the conversion of feeds formed by organic compounds inhigh-added-value products, or as molecular sieves for streamelimination/separation (for example, gas mixtures), by bringing thefeeds into contact with the material obtained.

According to a preferred embodiment, the material obtained in accordancewith the present invention may be used in the production of olefinsafter bringing it into contact with an oxygenated organic compound undercertain reaction conditions. Particularly, when methanol is fed, theolefins obtained are primarily ethylene and propylene. The ethylene andthe propylene may be polymerised to form polymers and co-polymers, suchas polyethylene and polypropylene.

According to another preferred embodiment, the material obtained in thepresent invention may be used as a catalyst in selective catalyticreduction (SCR) reactions of NOx (nitrogen oxides) in a gas stream.Particularly, the SCR of NOx will be performed in the presence ofreducing agents, such as ammonium, urea and/or hydrocarbons. Materialswhich have had copper atoms introduced by means of any known techniqueare particularly useful for this use.

Throughout the description and the claims, the word “comprises” andvariants thereof are not intended to exclude other technicalcharacteristics, additives, components or steps. For persons skilled inthe art, other objects, advantages and characteristics of the inventionwill arise, partly from the description and partly from the practice ofthe invention.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows the diffraction pattern of the material obtained in Example1 of the present invention.

The present invention is illustrated by means of the following examples,which are not intended to limit the scope of the invention.

EXAMPLES Example 1 Synthesis of CHA Using Tetraethylammonium as the OSDA

1037.2 mg of an aqueous solution of tetraethylammonium hydroxide (TEAOH,Sigma Aldrich, 35% by weight in water) are mixed with 477.1 mg of a20%-by-weight aqueous solution of sodium hydroxide (NaOH, Sigma-Aldrich,98%) and 34 mg of Milli-Q water. The mixture is homogenised by beingkept under stirring. Finally, 791.0 mg of zeolite Y (CBV-720, SiO₂/Al₂O₃molar ratio=21) are added, and the mixture is kept under stirring untilthe desired concentration is achieved. The composition of the final gelis SiO₂/0.047 Al₂O₃/0.2 TEAOH/0.2 NaOH/5 H₂O. This gel is transferred toa teflon-lined steel autoclave and heated at 160° C. for 7 days. Oncethis time has elapsed, the product obtained is recovered by means offiltration and washed abundantly with water. By means of X-raydiffraction, it is observed that the solid obtained presents thecharacteristic peaks of the CHA structure (see FIG. 1). The solid yieldobtained is greater than 85%.

The material is calcined at 550° C. for 4 h in an air atmosphere inorder to eliminate the organic matter retained inside it.

Example 2 Synthesis of CHA Using Tetraethylammonium as the OSDA

4494.4 mg of an aqueous solution of tetraethylammonium hydroxide (TEAOH,Sigma Aldrich, 35% by weight in water) are mixed with 2047.1 mg of a20%-by-weight aqueous solution of sodium hydroxide (NaOH, Sigma-Aldrich,98%) and 9525.0 mg of Milli-Q water. The mixture is homogenised by beingkept under stirring. Finally, 3670.2 mg of zeolite Y (CBV-712,SiO₂/Al₂O₃ molar ratio=12) are added, and the mixture is kept understirring until the desired concentration is achieved. The composition ofthe final gel is SiO₂/0.083 Al₂O₃/0.2 TEAOH/0.2 NaOH/15 H₂O. This gel istransferred to a teflon-lined steel autoclave and heated at 160° C. for7 days. Once this time has elapsed, the product obtained is recovered bymeans of filtration and washed abundantly with water. By means of X-raydiffraction, it is observed that the solid obtained presents thecharacteristic peaks of the CHA structure. The solid yield obtained isgreater than 85%.

The material is calcined at 550° C. for 4 h in an air atmosphere inorder to eliminate the organic matter.

Example 3 Synthesis of Triethylpropylammonium Hydroxide

12.8 ml of triethylamine (C₆H₁₅N, Sigma Aldrich, 99%) are dissolved in250 ml of acetonitrile (CH₃CN, Scharlau, 99%). This solution is keptunder stirring whilst 44 ml of 1-iodopropane (C₃HI, Sigma Aldrich, 99%)are added drop by drop. After the addition is completed, the mixture isheated under reflux at 80° C. for 3 days. Once this time has elapsed,the mixture is partially concentrated in the rotary evaporator and anexcess of diethyl ether (C₄H₁₀O, Scharlau, 99.5%) is added in order toprecipitate the final product triethylpropylammonium iodide, which isvacuum filtered and washed with diethyl ether, to obtain a yield of 88%.

Finally, ion exchange of the triethylpropylammonium halide is performedwith the corresponding hydroxide. To this end, a solution of 10 g oftriethylpropylammonium iodide in 73.7 g of water is prepared, and 37 gof the ion-exchange resin Amberlite (Amberlite IRN78, hydroxide form,Supelco) are added to this mixture. The mixture is kept under stirringovernight and, once this time has elapsed, it is vacuum filtered inorder to separate the final product, triethylpropylammonium hydroxide,from the resin. The solution obtained is titrated with hydrochloric acid(HCl, Sigma Aldrich, 0.1 M), resulting in a concentration of 7.1% byweight and 75% exchange.

Example 4 Synthesis of CHA Using Triethyl Propylammonium as the OSDA

3064.5 mg of a solution of triethylpropylammonium hydroxide (TEPrOH,7.1% by weight, prepared according to Example 3 of the presentinvention) are mixed with 274.0 mg of a 20%-by-weight solution of sodiumhydroxide (NaOH, 98%) in water. The mixture is homogenised by being keptunder stirring. Finally, 435.0 mg of zeolite Y (CBV-720, SiO₂/Al₂O₃molar ratio=21) are added, and the mixture is kept under stirring untilthe desired concentration is achieved. The composition of the final gelis SiO₂/0.047 Al₂O₃/0.2 TEPrOH/0.2 NaOH/5 H₂O. This gel is transferredto a teflon-lined steel autoclave and heated at 160° C. for 7 days. Oncethis time has elapsed, the product obtained is recovered by means offiltration and washed abundantly with water. By means of X-raydiffraction, it is observed that the solid obtained primarily presentsthe characteristic peaks of the CHA structure.

The material is calcined at 550° C. for 4 h in an air atmosphere inorder to eliminate the organic matter.

Example 5 Preparation of the Cu-Exchanged Zeolite CHA (Cu-CHA)

The sample synthesised and calcined according to the method explained inExample 1 is washed with 150 g of a 0.04 M aqueous solution of sodiumnitrate (NaNO₃, Fluka, 99% by weight) per gram of zeolite.

33.63 mg of copper acetate [(CH₃COO)₂Cu.H₂O, Probus, 99%] are dissolvedin 30 g of water, and 303.3 mg of the previously washed zeolite areadded. The suspension is kept under stirring for 24 h. Once this timehas elapsed, the product obtained is recovered by means of filtrationand washed abundantly with water. Finally the material is calcined inair at 550° C. for 4 h.

Example 6 Catalytic Assay of the SCR Reaction of NOx

The catalytic activity of the Cu-CHA sample synthesised according toExample 5 of the present invention in the selective catalytic reductionof NOx is studied using a fixed-bed tubular quartz reactor 1.2 cm indiameter and 20 cm long. In a typical experiment, the catalyst iscompacted into particles with a size ranging between 0.25-0.42 mm; theseare introduced into the reactor and the temperature is increased until550° C. are reached (see the reaction conditions in Table 1);subsequently, this temperature is maintained for one hour under a flowof nitrogen. Once the desired temperature has been reached, the reactionmixture is fed. The SCR of NOx is studied using NH₃ as the reducingagent. The NOx present in the reactor outlet gas is continuouslyanalysed by means of a chemiluminiscent detector (Thermo 62C).

TABLE 1 Reaction conditions for the SCR of NOx Total gas flow (ml/min)300 Catalyst load (mg) 40 NO concentration (ppm) 500 NH₃ concentration(ppm) 530 O₂ concentration (%) 7 H₂O concentration 5 Tested temperaturerange (° C.) 170-550

The catalytic results of the Cu-CHA catalyst prepared according toExample 5 of the present invention are summarized in Table 2.

TABLE 2 Conversion (%) of NOx at different temperatures (200° C., 250°C., 300° C., 350° C., 400° C., 450° C., 500° C.) using the Cu-CHAcatalyst prepared according to Example 5 of the present inventionConversion (%) of NOx at different temperatures 210° C. 250° C. 300° C.350° C. 400° C. 450° C. 500° C. 550° C. Example 5 94.9 100.0 100.0 100.0100.0 99.7 95.5 90.8

1-30. (canceled)
 31. A zeolite material with the CHA structure havingthe diffraction pattern as shown in FIG. 1, and having the followingmolar composition after being calcined:n X₂O₃:YO₂ where X is a trivalent element; Y is a tetravalent element;and n ranges between 0 and 0.1.
 32. The zeolite material with the CHAstructure according to claim 31, wherein the tetravalent element Y isselected from silicon, tin, titanium, germanium, and combinationsthereof.
 33. The zeolite material with the CHA structure according toclaim 31, wherein the tetravalent element Y is silicon.
 34. The zeolitematerial with the CHA structure according to claim 31, wherein thetrivalent element X is selected from aluminium, boron, iron, indium,gallium, and combinations thereof.
 35. The zeolite material with the CHAstructure according to claim 31, wherein the trivalent element X isaluminium.
 36. A material which is obtainable by eliminating the organiccontent retained inside zeolite material according to claim 31 by meansof a heat treatment at temperatures ranging between 100° C. and 1000° C.for a period of time ranging between 2 minutes and 25 hours.
 37. Amaterial which comprises the zeolite material with the CHA structureaccording to claim 31 having ion exchanged cations by conventional ionexchange techniques.
 38. The material according to claim 37, wherein theion exchanged cations are selected from metals, protons, protonprecursors, and mixtures thereof.
 39. The material according to claim38, wherein the ion exchanged cations are of a metal selected from rareearth metals, metals of groups IIA, IIIA, IVA, VA, IB, BB, III, IVB, VB,VIB, VIIB, and VIII, and combinations thereof.
 40. The materialaccording to claim 39, wherein the metal is copper.
 41. A method forconverting, eliminating, or separating feeds formed by organic compoundsin a high-added-value product, which comprises bringing said feed intocontact with a zeolite material according to claim
 31. 42. A method ofproducing an olefin, which comprises contacting an oxygenated organiccompound with a zeolite material according to claim
 31. 43. A method ofselective catalytic reduction (SCR) of NOx (nitrogen oxides) in a gasstream, which comprises contacting the gas stream with a zeolitematerial according to claim
 31. 44. A method for converting,eliminating, or separating feeds formed by organic compounds in ahigh-added-value product, which comprises bringing said feed intocontact with a material according to claim
 36. 45. A method of producingan olefin, which comprises contacting an oxygenated organic compoundwith a material according to claim
 36. 46. A method of selectivecatalytic reduction (SCR) of NOx (nitrogen oxides) in a gas stream,which comprises contacting the gas stream with a material according toclaim 36.